Organic photoconductors sensitized by free radical liberators and organometallic compounds

ABSTRACT

A photosensitive material suitable for electrophotography is composed mainly of a free radical former capable of producing free radical by a radiation energy (F) and an organic photoconductive material (OPH) treated with a radiation energy in the presence of an organometallic compound (OM). If desired, a dye base compound or an organic colorization component may be added thereto. The photosensitive material may be produced by applying a radiation energy to a formulation containing F, OPH and OM.

United States Patent Endo et al. Nov. 12, 1974 [5 ORGANIC PHOTOCONDUCTORS 3,490,907 l/l970 Schenck ct ill 96/90 R vSENsfnZffl) BY FREE RADICAL 3,489 568 l/l970 Hackman et al....,. 96/90 R LIBEKATOBS QRGANOMETALLIC ,2; 32(9) Holslead .4 V COMPQUNDS 31598584 8/1971 [75] Inventors: Ichiro Endo, Tokyo; Teruo JYaaprlllfinouchi, FUJISaWZI, both of 3:352:772 H967 3,421,89l l/l969 [73] Assignee: Canon Kabushiki Kaisha, Tokyo, 3331130 1 W966 Japan 3.501476 3/1970 3,102,029 8/1963 ltano et al 96/90 R [22] FlleClZ May 3, 1973 3101810 9/1963 Sprague et al. 96/90 R X 21. A l. N 356 805 l 1 PP O Primary ExaminerRoland E. Martin, .lr. Related US. Application Data [63] Continuation of'Ser. No. 111,626 Feb. l. l97l, Fat. [57] ABSTRACT A photosensitive'matcrial suitable for electrophotog- [52'] U S 96/1 6 96/1 5 96/90 R raphy is composed mainly of a free radical former ca-' 6 8 pable of producing free radical by a radiation energy 96/73 (F) and an organic photoconductive material/OPH) [51] Cl G03g 5/06 treated with a radiation energy in the presence of an Fie'ld 1 6 35 l organometallic compound (OM). If desired, a dye I base compound or an organic colorization component 96/115 115 90 204/5924 may be added thereto. The photosensitive material [561 References Cited may be produced by applying a radiation energy to a formulation containing F, OPH and OM.

40 Claims, No Drawings ORGANIC PHOTOCONDUCTORS SENSITIZED BY FREE RADICAL LIBERATORS AND ORGANIMETALLIC COMPOUNDS This'is a continuation, of application Ser. No. 111,626, filed Feb. 1, 1971, now US. Pat. No. 3,765,883.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a photosensitive material and preparation of said photosensitive material. More particularly, this invention relates to photosensitive material mainly containing an organic photoconductive material and a free radical former capable of producing a free radical by exciting with a radiation energy subjected to a radiation energy in the presence of an organometallic compound and a method of producing said photosensitive material. This application is related-to co-pending application Ser. No. 111,626 filed Feb. 1, 1971. v

2. Description of the Prior Art As electrostatic photographic photosensitive materials, there have been used metallic selenium and'selen alloys for indirect electrostatic photography and metal lic oxides such as zinc oxide for direct electrostatic photography, and they are widely used for reproduc tion apparatus. On the contrary, organic photoconductive materials are far better than selenium and zinc oxide in points of transparency, flexibility, light weight, film shapability, selectivity of charging polarity, and surface smoothness, but organic photoconductive materials have not been practically used for electrostatic photography. This is due to that the photosensitivity of organic photoconductive materials is remarkably lower than that of selenium and zinc oxide and, therefore, a strong light source is necessary for image-wise exposure after charging. As organic photoconductive materials, there have been known, for example, condensed polynuclear aromatic compounds such as anthracene, pyrene, perylene and the like, heterocyclic compounds such as triphenyl pyrazoline derivatives, acyl hydrazone derivatives and high polymers such as poly-N- vinylcarbazole. It has been'recently contemplated to enhance the photosensitivity of the above mentioned conventional photoconductive materials of low sensitivity by using organic syntheticmeans. As the result,

V several useful photoconductive materials have been found. For example, they are brominated poly-N- vinylcarbazole disclosed in Japanese Patent Publication No. 25230/1967, poly-3,6-diiodo-9-vinylcarbazole disclosed in Japanese Patent Publication No. 7592/ 1968 poly-N-vinyl-3-aminocarbazole disclosed in Japanese Patent Publication No. 9639/1967, and polyvinylanthracene disclosed in Japanese Patent Publication No. 2629/1968. However, these photoconductive materials alone are not of high photosensitivity and therefore, they are used together with a spectral sensitizing dye for practical use. For example, a brominated polyvinylcarbazole is combined with a certain triaryl carbonium salt dye to give a photosensitivity comparable with that of zinc oxide sensitized by dye. As are clear from the above mentioned example, the organic photoconductive materials and the sensitizing dye combined therewith for sensitization are usually prepared by special and complicated organic syntheses and purification. Therefore, even if thereis obtained high sensitivity, there remain economical and practical problems.

The prevent'inventors have now found that organic photoconductive materials can be sensitized by a simple sensitizing treatment to give a high sensitivity comparable with or higher than that of conventional selenium or zinc oxide (dye-sensitized).

In'a printing-out recording material known as free radical system, there is used a free radical former capable of producing free radical when excited by radiation energy, but such photosensitive material or recording material are low in stability. This is due to the free radical former used. For example, when as the free radical former, a polyhalogen compound such as carbon tetrabromide is employed, unreacted carbon tetrabromide is essentially present in a photosensitive layer of the photosensitive material or recording material and carbon tetrabromide is so volatile, unstable and poisonous that such photosensitive material or recording material can not be practically used.

According to the present invention it is possible to solve such drawbacks and provide a highly sensitive, economical and chemically stable photosensitive material for electrostatic photography.

SUMMARY OF THE INVENTION The photosensitive material according to this inven tion is composed mainly of a free radical former capable of producing free radical by exciting with a radiation energy and an organic photoconductive material irradiated with a radiation energy in the presence of an organometallic compound.

According to another aspect of this invention, the photosensitive material may additionally contain a dye base compound and/or an organic colorization component. 1

According to a further aspect of this invention,-the above mentioned photosensitive material may be prepared by applying a radiation energy, if desired, together with heat to the composition containing the above mentioned ingredients.

According to still another aspect of this invention, a photosensitive member may be produced by applying a radiation energy to the above mentioned ingredients present on a support.

An object of this invention is to provide an electrostatic photosensitive material highly sensitized and method for preparing the same.

Another object of this invention is to provide a highly sensitive organic photoconductive photosensitive material for electrostatic photography comprising a free radical former capable of producing free radical by a radiation energy and an organic photoconductive material subjected to a radiation energy in the presence of organometallic compound, and method for production thereof.

A further object of this invention is to provide an economical and highly sensitive organic photoconductive photosensitive material which is free from complicated organic syntheses and purification step and can be ob tained by a simple sensitizing treatment, and method for production thereof.

Still another object of this invention is to provide a chemically stable and highly sensitive organic photosensitive material and method for production thereof.

3 DETAILED DESCRIPTION tuted 9-vinylcarbazole copolymer such as 3-bromo-9- vinylcarbazole copolymer, brominated 9- vinylcarbazole copolymer and 3 ,6-dibromo-9- .vinylcarbazole copolymer, poly-N-vinyl-3- aminocarbazole, bromine substituted poly-9- vinylcarbazole such as poly-3-bromo-9-vinylcarbazole, poly-3,6-dibromo-9-vinylcarbazole and brominated-N- vinylcarbazole, iodine substituted poly-9- vinylcarbazole such as 3-iodo-9-vinylcarbazole copolymer and poly-3,6-diiodo-9-vinylcarbazole, iodine substituted 9-vinylcarbazole copolymer such as 3-iodo-9- vinylcarbazole copolymer, poly-3-benzylideneamino-9- vinylcarbazole, a,w-bis-(N-carbazole)-alkane derivative, vinylanthracene-N-vinylcarbazole copolymer, and 2- (or 3-) vinyl-9-alkyl carbazole homopolymer or copolymer wherein alkyl is primary alkyl group such as methyl, ethyl and propyl.

B As aromatic amino derivatives, there may be mentioned, for example, aminopolyphenyl, allylideneazine, N,N-diallyl-N,N-dibenzyl phenylenediamine, N,N,N- ',N-tetrabenzyl-p-phenylenediamine, N,N'-diphenylp-phenylenediamine, N,N-dinaphthyl-pphenylenediamine, and 4,4-bisdimethylaminobenzophenone.

C. As diphenylmethanes and triphenylmethanes, there may be mentioned, for example, diphenylmethane dye leuco base and triphenylmethane dye leuco base. D, As compounds having heterocyclic ring, there may be mentioned, for example, oxadiazole,

aminothiazole, 4,1,2-triazole, imidazolone, oxazole, imidazole, pyrazoline, imidazolidine, polyphenylene thiazole, l,6-methoxyphenazine, and pyrazolinopyrazoline derivatives.

E. As compounds having a condensed ring, there may be mentioned, for example, benzthiazole, benzimidazole, benzoxazole derivatives such as 2-(4'-diamino-' H. As vinyl polymers (excluding polyvinylcarbazole), there may be mentioned, for example, a-alkylacrylic acid amide polymer, polyvinylacridine, poly-[1,5- diphenyl-3-(4-vinylphenyl)-2-pyrazoline], poly( l ,5- diphenyl)-pyrazoline, polyacenaphthylene, nuclear substituted polyacenaphthylene, polyvinylanthracene, and poly-2-vinyldibenzthiophene.

I. As organic photoconductive oligomers, there may be mentioned, for example, compound having the formula wherein Z, M and n are each 0 or 1, and l m 2 N. For example, as a five ring compound, there may be mentioned p-bis(2-phenyl-4-thia2olyl) benzene; as a seven ring compound, 2,4-bis[4-(2-phenyl-4-thiazolyl)- phenyl] thiazole; as a nine ring compound, l,4-bis[4- {4-(2-phenyl-4-thiazolyl)-phenyl}thiazolylIbenzene. Among these organic photoconductive materials, there are preferably used vinylcarbazole and its derivatives, aromatic amino derivative, and diphenylmethane and triphenylmethane derivatives. A free radical former employed in this invention is a material capable of producing a free radical by excitation with a radiation energy. A free radical former can be selected from the following classes of widely ranged substances.

A. As polyhalogen containing compounds, there may be used a compound of the general formula:

wherein R represents hydrogen, alkyl, halogen atom selected from Cl, Br and I,

wherein R, represents substituted or unsubstituted al kyl, aryl or heterocyclic group; X, Y and Z are similar or dissimilar, and hydrogen, alkyl or halogen atom selected from Cl, Br and I, at least one of X, Y and Z is halogen atom, for example, CBr C14, CHI C CI CBrCl CCl CHBr CHCl C Br C HBr C H CBr CIBr CICI CHlCl CHIBr CBrCl CHBrCl 2,2,2-trichlorotoluene, 2,2,2-tribromo acetophenone, 1,1, l -tribromo-2-methyl-2-propanole, l,l,2,2-tetra bromoethane, 2,2,2-tribromoethanole, cHgclg, CH BI'g, CH2I2, BI'CHgCHgBI', CH CI-ICl CH CHBr CHCl CHCl ClCH=CHCl, CHCl=CCl Br(CH ),,Br, Br(CH Br, Br(CH ),,Br and Br(CH ),,Br; halogenated organic sulfoxidc such pentabromodimethylsulfoxide and hexabromodimcthylsulfoxide, halogenated organic sult'one compound such as hexabromodimethylsulfone, trichloromethyl- 4-chlorophenyltrichloromethyl bonyl pound omethyl-parachlorophenyl sulfone, tribromomethylparanitrophenyl sulfone, 2-trichloromethyl-benzoxathiazolyl 'sulfone, 4,6-dimethylpyrimidyl-2 tribromomethyl sulfone, tetrabromodimethyl sulfone, 2,4-dichlorophenyltrichloromethyl sulfone, Z-methyl- 4-chlorophenyl trichloromethyl sulfone, 2,5-dimethylsulfone, 2,4- dichlorophenyl tribromomethyl sulfone, and bromomethyldibromomethylsulfone. B. As carbonyl compounds, there maybe mentioned, for example, vicinal polyketaldonyl compounds, a-caralcohols, acryloin ethers, oz-hydrocarbonsubstituted acryloins, polynuclear quinones. C. As sulfur compounds, there may be mentioned, for example, alkyldisulfide, aralkyldisulfide, aryldisulfide, aroyldisulfide, acryldisulfide, cyclic alkyldisulfide, mercaptane, thiole, metalmercaptide, dithiocarbamates, O-alkylxanthene esters, and thiuram derivatives. D. As a peroxide compound, there may befor example, hydroperoxide, dialkylperoxide, diacrylperoxide and diaroylperoxide. E. As azo and diazo compounds, there may be mentioned, for example, azonitrile compound, diazo comsuch as p-nitrobenzene diazonium-pchlorobenzene sulfonate.

Among these free radical formers, a compound giving an especially excellent result is a polyhalogen containing compound.

Therepresentative organometallic compounds used in this invention are alkylmetallic compound, arylmetallic compound, alkylarylmetallic compound and cyclopentadienyl-metallic compound. Metals in alkylmetallic compound, arylmetallic compound and alkylarylmetallic compound are metal elements in -the Groups W3 and VB of the Periodic Table. The metals are preferably Ge, Sn, Pb, P, As,Sb and Bi. The metal in cyclopentadienyl compound is transition metal elements ,in the Groups lllA, lVa, Va, VlA, VIIA and VlIlA. The transition metal elements as the Group IllA element are Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Er and Yb; as the Group IVA element Ti, Zr and Hf; as the Group VA element V, Nd and Ta; as the Group VlA element Cr, Mo, W and U; as the Group VllA element Mn,.Tc and Re; and as the Group Vl-lIA element Fe,

Co, Ni and Ru.

The examples for these organometallic compound are the followings/ As the alkylmetallic compound, arylmetallic commay be mentioned, for example, cyclopentadienyl compounds ofcandium, yttrium, lanthanum, cerium,

praseodymium, neodymium, Samarium, gadolinium, dysprosium, erbium and ytterbium. As an organometallic compound having the Group IVA transition elements, there may bementioned, for example,'bis (cy.-

6 clopentadienyl) titanium, dihalogenated bis(cyclopentadienyl) titanium, bis (cyclopentadienyl) titanium diaryl, and bis (cyclopentadienyl) zirconium dibromide. As an organometallic compound having the Group VA transition element, there may be mentioned, for example, bis (cyclopentadienyl) vanadium dihalide, bis (cyclopentadienyl) niobium tribromide, bis (cyclopentadienyl) tantalum tribromide, bis (cyclopentadienyl) vanadium, and cyclopentadienyl vanadium tetracarbonyl.

As an organometallic compound having the Group VIA transition element, there may be mentioned, for example, bis (cyclopentadienyl) chromium, bis (cyclopentadienyl)- u-pentacarbomonooxidebimolybdenum, bis (cyclopentadienyl)- u-hcxacarbonmonooxide-bitungsten, tris (cyclopentadienyl) uranium chloride.

As an organometallic compound having the Group VllA transition element, there may be mentioned, for example, bis (cyclopentadienyl) manganese, and hydrogenated bis (cyclopentadienyl) rhenium.

As an organometallic compound having the Group VlllAtransition element, there may be mentioned, for example, bis (cyclopentadienyl) iron [ferrocene], bis (cyclopentadienyl) iron dicarbonyl, cyclopentadienyli- .ron dicarbonyl chloride, cyclopentadienylirondicarbonyl cyanate, bis (cyclopentadienyl) cobalt bromide, bis (cyclopentadienyl cobalt [cobaltocene], cyclopentadienyl cobalt dicarbonyl, bis (cyclopentadienyl) nickel [nickelocene], cyclopentadienylnickelnitrosyl, bis (cyclopentadie-nyl) ruthenium and his (cyclopentadienyl) ruthenate.

One or more of the organometallic compounds may be used. Among the above-mentioned organometallic compounds, there are preferably used triphenylbismuthine, triphenylphosphine, tetraphenylallene', ferrocene and cobaltocene.

The radiation energy source used in .this invention-is selected depending upon organometallic compounds, free radical formers, organic photoconductive materials and/or solvent used. Any kind of light source may be used as far as it can produce free radical from a free radical former in the sensitization system. Preferably a light source emitting a large amount of ultraviolet ray or near ultraviolet ray such as mercury (low pressure, high pressure or super high pressure), metal halide lamp and xenon lamp is used. If desired, a radiation energy such as ultraviolet ray can be applied together with heat to accelerate the decomposition of free radical formers by selecting the temperature at which the radiation energy is applied and the time of irradiation in such a manner that there are balanced the degree of sensitization and undesirable secondary effects such as remarkable colorization and gellation. Furthermore, it is clear that the decomposition of free radical former and the accompanying chemical reaction can be controlled by adjusting the time of applying'the radiation energy. The effective wave length of radiation energy is, for example, illustrated below.

Halogen compound 300 400 my Carbonyl compound 360 38!) m Organic sulfur compound 280 401) m Peroxide 300 400 mp, Azo compound Among them,.effectiv.e wave length for some halogen compounds is shown below.

The sensitization treatment may be effected as follows. An organic photoconductive material, a free radical former and an organometallic compound are brought into coexistence to form a uniform solution by using an appropriate solvent and a radiation energy is applied to the resulting solution for sensitization treatment. In this case, if an organometallic compound is not used it is very difficult to select an appropriate solvent since the solvent should have a sufficient solubility to the organic photoconductive material and the free radical former, and furthermore such a solvent which reduces the sensitization effect should be avoided. For example, in case of using poly-N-vinylcarbazole as organic photoconductive material and carbon tetrabromide as free radical former, benzene and monochlorobenzene can enhancethe sensitization effect while tetrahydrofuran and dioxane reduce the sensitization effect.

The present inventors have found that the reduction of sensitization effect caused by solvent is remarkably weakened by incorporating a small amount of an organometallic compound in thereaction system. For example, there may be used methylene chloride, chloroform, toluene and xylene which are usually not preferable, and further tetrahydrofuran and dioxane which are extremely unfavorable can also be sufficiently used. Thus the selection range of solvent is very broadened. The use of organometallic compound results in high sensitivity. The sensitizing effect of the organometallic compounds is illustrated in the Examples appearing later. When a solution containing a free radical former and an organic photoconductive material has a color or the solution contains additionally a dye base compound or an organic colorizationcomponent, the sensitization effect can be visually observedtsince the colorization of the solution is markedly accelerated.

The sensitization treatment may be carried out by various methods such as, for example, applying a radiation energy to a solution comprising an organometallic compound and a free radical former followed by mixing with a solution of an organic photoconductive solution, or applying a radiation energy to each of a solution containing-a free radicalformer and an organic photoconductive materialand asolution containing a free radical former and an organometallic compound followed by mixing these two solutions, or applying a radiation energy to a solution containing an organic photoconductive material, a free radical former and an organometallic compound coated on a base support. Furthermore, a photosensitive material of higher sensitivity can be obtained by additionally incorporating a dye base compound or organic colorization component thereto. Particularly, in case of applying a radiation energy to a solution containing an organic photoconductive material, a free radical former, an organometallic compound and, if desired, a dye base compound and/or an organic colorization component which is coated on a base support, any solvent can be selected as far as the solvent can dissolve the organic photoconductive material. This free selection of solvent is very valuable.

The change caused by applying a radiation energy to organic photoconductive material, free radical former and organometallic compound is considered to occur in the following sequence.

Assuming that the free radical former is a polyhalogen compound of the formula R CX where R is hydrogen, halogen, alkyl or aryl (substituted or unsubstituted) and each X may be, the same or different, chlorine, bromine or iodine, when the polyhalogen compound is exposed to a sufficient amount of radiation energy, the following reaction proceeds:

The X thus formed (halogen free radical) extracts hydrogen from a medium to form secondarily HX (halogen acid) as follows.

X- HX the R-CX (organic free radical) is considered as a chain carrier causing reactions (1) and (2) above as chain reaction.

When an organometallic compound (M) is present in the reaction system, the radical formation efficiency by a radiation energy is increased as shown in the following formula:

It is considered that the organometallic compound works as a reaction accelerator or catalyst.

Therefore, the-reactions shown in Formulas l and (2) can be effectively caused and the reaction time is shortened by-the action of the organometallic compound and simultaneously the reaction'conditions such as selectivity of solvent, tolerable amounts of impurity, and temperature range for. reactions of Formulas (l) and (2) can be broadenedAnd further the addition of organometallic compound results in improvement in photosensitivity.

According to the present invention, the abovementioned organometallic compound and halogen compound are added to a solution of organic photoconductive material and the resulting solution is subjected to a radiation energy sufficient to cause the reactions in Formulas (l) and (2) to sensitize remarkably the organic photoconductive material. It has now been found that the above mentioned sensitizing treatment can improve photosensitivity of photosensitive materials for electrophotography, but the mechanism of sensitization is not yet fully understood. The amount of the free radical former used in this invention is appropriately selected depending upon each particular photoconductive material and amount of radiation energy. ln general, the amount of the free radical former is preferably 1 30 percent by weight. The amount of organometallic compound used in this invention is appropriately selected depending upon each particular photoconductive material, free radical former, and amount of radiation energy. In general, the amount of the organometallic compound preferably ranges from 10 to 10 percent by weight.

When the organic photoconductive material itself has film shapability, it is not necessary to use a binder resin or plasticizer, but when it lacks in film shapability, it is desirable to use a binder resin of 30 percent ,cyanine quinolylidenepropenyl] quinoline, 2-[2-methyl-3-(3- compound by weight based on the photoconductive material. For

' the purpose of improving the property of film, 100

I lene, p-terphenyl and diphenyl.

In order to further enhance photosensitivity of the photosensitive material for electrography obtained by this invention and adjust the spectral sensitivity characteristics, it is effective to add a dye sensitizer or Lwiss acid usually used in electrophotography singly or in combination. Furthermore, it is also effective for increasing photosensitivity of the photosensitive material to add a dye base compound capable of forming a coloring matter by the reaction with a free radical former caused by a radiation energy. In addition, it is effective to add an organic colorizat-ion component capable of forming a coloring material by the reaction with a free radical former caused by a radiation energy. These dye base compound and organic colorization components can produce-a far higher sensitization effect than that obtained by usual dye sensitizer.

, Representative dye base compounds are shown below.

As leuco base or carbinol base, there may be mentioned, for example, leuco base of triphenylmethane dye such as leuco malachite green, leucocrystal violet, leuco methylviolet,.leuco opal blue; carbinol base of triphenylmethane dye such as carbinol crystalviolet, carbinol methylviolet, leuco base or carbinol base of diphenylmethane dye having the formula where R R R and R represents a member selected from the group consisting of hydrogen, alkyl, aralkyl and aryl (substituted or unsubstituted), when X is -H, leuco base, when X is OH, carbinol base; such as Michlers hydrol, styryl dye such as 4-(4- dimethylaminophenyl-l,3-butadienyl)-quinoline, 4-pdimethylaminostyrylquinoline, Z-p-dimethylaminostyrylquinoline and 2-p-dimethylaminostyrylquinoline,

dye such as 2-[3-ethyl-2( 1H)- ethyl-2( 3H )-benzothiazolylidene propenyllbenzothiazole, benzothiazolylideneamino) vinyl]quinoline, 4-( l-ethyl- 2( ll-l)-quinoly]deneamino-)quinone, 2(pdimethylaminobenzylidene) aminoquinoline, and 4-('pdimethylaminopheny-limino )-cyanomethylquinoline, merocyamine dye 'base such as 3-ethyl-5-[(3-ethyl- 2 (3H)-ben2oxazolylidene] rhodanine, l-ethyl-3-[(3- ethyl-2(3H')-benzoxazolylidene]-oxyindole, and 4-[(3- ethyl-2(3HFbenzoxazolylidene)-ethylindene]-3- phenyl-5(4l-l)-isooxazolone, leuco dihydroanthracene such as 2,7-bis(dimethylamino )--pdimeth-yla-minophenyl9,lOdihydro-9,9-

dimethylanthracene and 2,7-.bis(dime.thylamino) 9,l0-

dihydro-9,9-dimethylanthracene. There may be mentioned the following compounds as organic colorization components used in this invention.

As an arylamines there may be mentioned, for example, a compound of the general formula:

R-N-R wherein R represents a member selected from the group consisting of' hydrogen, alkyl, alkenyl, aralkyl and ,aryl (substituted or unsubstituted), R, and R are similar or dissimilar, a member selected from the group consisting of hydrogen, alkyl, alkenyl, aralkyl, alkoxy, halogen and dialkylamino.

As such a compound there may be mentioned, for example, carbazole, N-ethylcarbazole, N- methylcarbazole, N-phenylcarbazole, N-

benzylcarbazole, N-vinylcarbazole, 3,6-dibromo-N- vinylcarbazole, 3-chloro-N-ethylcarbazole, 3-chloro- N-vinylcarbazole, 3-iodo-N-vinylcarbazole and 3- dimethylamino-N-ethylcarbazole.

C. lndoles having the general formula:

wherein R represents a member selected from the group consisting of hydrogen, alkyl, aralkyl and aryl (substitutedor unsubstituted), each of R is similar or dissimilar, a member selected from the group consisting of hydrogen, alkyl, alkoxy, halogen and dialkylamino.

As such a compound, there may be mentioned, for V 1 1 l -l,3,4-triazole, 2,5-bis-[4-N,N-diethylaminophenyl-l ']-l ,3,4-triazole, 2,5-bis-[4'-aminophenyl-l '1- l ,4triazole and 2,5-bis-[4'-N-ethylaminophenyl-l '1- l ,4-triazole. E. As imidazoles there may be mentioned, for example, 4-(4'-dimethylaminophenyl)-5-(4"-chlorphenyl)- imidazole, l-methyl-2-(diethylaminophenyl)-4,5- diphenyl-imidazole, 4-(4-dimethylaminophenyl)-5- -phenyl-imidazole and 2-(4'-dimethylaminophenyl)- 4,5-diphenyl-imidazole.

- G. As pyrazolines, there may be mentioned, for exam- -for example, ortho-tridine, N,N-diphenylbenzidine,

naphthdidine, andbenzidine. J. As 1,3-diphenyl-tetrahydroimidazoles, there may be mentioned, for example, l,3-diphenyl-2-(4'- dimethylaminophenyl )-tetrahydroimidazole, 1,3- diphenyl-2-styryltetrahydroimidazole and 1,3-

diphenyl-2-styryltetrahydroimidazole.

K. As phenazine compounds, there may be mentioned, for example, 1,6-dimethoxyphenazine, and 1,6- dimethylphenazine. L. As acridine compounds, there may be mentioned, for example, 3,6-bis(diamino)acridine, 3,6-bis(dimethylamino)-acridine and acridine.

' M. As acylhydrazone derivatives, there may be mentioned, for example, compounds having the formulae CO-hH-N=CH N O OCQ-NH-N;CH-ON 3 N. As quinoxaline compounds there may be mentioned, for example, 2,3-bis-(4'-methoxyphenyl)-6- aminoquinoxaline, 2-p'henyl-3-(4-dimethylaminophenyl)-6-chloroquin0xaline, and 2-phenyl-3-(4'- dimethylaminophenyl)-6,7benzoquinoxaline.

O. As-arylideneazine compounds containing N-disubstituted-amino 'group, there may be mentioned, for example, bis-4,4-diallyl-aminobenzylideneazine, bis- 12 4,4-diethylamino-2,2-dimethylbenzylideneazine, bis- 4,4-dibenzylaminobenzylideneazine, and bis-4,4-arylmethylaminobenzylideneazine.

P. As pyridine and quinoline compounds, there may be mentioned, for example, 2-[ l ,3-diox0hydrindcnyl- (2)]quinoline, 2-[4-chlor-l,3-dioxohydrindenyl- (2)]quinoline, 2-[1,3-dioxohydrindenyl-(2)]pyridine, and 4-methyl-2-[ l ,3-dioxohydrindenyl-( 2)]pyridine.

Q. As ethylene derivatives, there may be mentioned, for example, compounds having the formulae l l l l c a ooc-c -c-O c= c-cooc a R. As spiropyrans, there may be mentioned, for example, l,3,3-trimethylindolinobenzopyrylspiran, 1,3,3- trimethylindolino-6-nitrobenzopyrylspiran, 1,3 ,3- trimethylindolino-6-nitro-8-methoxybenzopyrylspiran and l,3,3-trimethylindolino-6-methoxy-8' nitrobenzopyrylspiran.

According to the present invention, a photosensitive material may be prepared by applying a radiation energy simultaneouslywith heat to a free radical former capable of producing free radical by a radiation energy and an organic photoconductive material in the presence of an organometallic compound; or applying a radiation energy to a solution system containing a free radical former capable of producing free radical by a radiation energy, an organic photoconductive material and an organometallic compound; or applying a radiation energy to a solution system containing a free radical former capable of producing free radical by a radiation energy and an organometallic compound and mixing the solution system thus treated with a solution system containing at least an organic photoconductive material; or mixing a solution system containing a free radical former capable of producing free radical by a radiation energy, an organic photoconductive material and an organometallic compound irradiated by a radiation energy with a solution system containing a free radical former and, if desired, additionally an organometallic compound irradiated by a radiation energy.

in the above preparation methods, a dye base compound and/or anorganic colorization components may be added to the system.

According to a method of producing a photosensitive member of this invention, a solution containing an organic photoconductive material, a free radical former and an organometallic compound subjected to or to be subjected to-a sensitizing treatment by using a radiation energy may be applied to a transparent or opaque sup- I port by conventional coating methods such as roll coating method, wire-bar coating method, air-knife method and the like. The radiation energy may be applied to the solution before or after the solution is coated on a support. For example, a radiation energy is applied to the solution coating while the coating is being continuously formed followed by drying. Furthermore, if desired, a dye base compound or an organic ccolorization component maybe added at this stage.

The method of producing a photosensitive member according to this invention is simple and of high efficiency.

Some'examples of this production of photosensitive member are shown below.

l. A formulation solution mainly containing an organometallic compound, an organic photoconductive material and a free radical former is coated on a support and then irradiated by a radiation energy sufficient to cause a remarkable sensitization in the resulting coating layer.

2. The formulation solution as in item (1) above is coated on a support, subjected to a radiation energy sufficient to cause a remarkable sensitization in the resulting coating layer and dried while the sensitization in the coating layer is accelerated.

3. The formulation solution as in item (1) above is coated on a support and simultaneously photo energy and thermal energyare applied to the coating.

4. The formulation solution as initem (1) above is coated on a support and simultaneously photo energy and thermal energy are applied to the coating, and then the resulting coating is dried by a thermal energy.

The thickness of the resulting photoconductive layer on the support may be. adjusted to a range of from several microns to several tens microns. For usual purposes, it is less than microns and several microns.

As the support, there may be used metal sheet such as aluminum, copper, zinc-and silver, paper treated in sucha manner that a solvent does not permeate, aluminum laminate paper, synthetic resin film in which a surfactant is incorporated, glass on which surface a metal, metal oxide or. metal halide is'deposited by the vapordeposition, paper and synthetic resin films such as polyethylene, polypropylene, polyethylene terephthalate,

polystyrene, polyvinyl chloride, ethyl cellulose, cellulose acetate and polyester. In general, any support having a surface resistivity lower than that of the photo-' conductive layer may be used. In other words, such material having a resistivity of lower than 10%, preferably lower than 10 9 may be used.

latent image thus formed is developed with a negatively charged toner by, for example, a magnet brush developing method, cascade developing method or a furbrush developing method to produce the positive image. This image may be flxed by heating or passing it through an appropriate solvent vapor. Liquid developing method may also be used. In this case, althrough the liquid developer as necessary constituents a coloring component and a carrier liquid, it is possible to add to it a controlling agent and an agent improving fixing property when desired. Further, the electric charge applied by corona charging may be a positive charge or a negative charge.

The following examples are given for illustrating the present invention, but should not be construed as limitation.

Example 1 Poly-9-vinylcarbazole (Luvican M-l70, trade name, supplied by Badische Anilin und Soda Fabrik) 8 g. Carbon tetrabromide 400 mg. Triphenylbismutin 8 mg.

' Benzene 200 ml.

To a solution comprising the above ingredients was applied a light irradiation for 5 minutes by using a photochemical reactor having a 100 watt high pressure mercury lamp produced by Ushio Denki Kabushiki Kaisha (When the solution excluding triphenylbismutin is used, the irradiation time for producing the same photosensitivity was as long as 15 minutes). The solution thus treated was applied,- in an amount of about 5 g/m as solid matter, to a base paper g/m subjected to a solvent permeation inhibiting treatment by coating polyvinyl in an amount of about 2 g/m and then dried for 5 minutes to form a photosensitive paper. Then the resulting photosensitive paper was given an uniform negative charge of about 380 V by corona charging using a charging apparatus of about 5.5 KV, contacted with an original positive film, exposed to a 150 watt tungsten lamp at lux.sec, and soaked in a liquid developer for positive image to produce positive images of high fidelity to the original image.

When a solution not containing triphenylbismutin was employed, the required exposure amount was about 250 lux.sec.

When the solution containing the above-mentioned ingredients was coated on the above-mentioned base paper and irradiated with a high pressure mercury lamp of 100 watt at a distance of mm for 5 seconds, the resulting photosensitive paper also gave a positive image of high fidelity to the original image under the reproduction conditions similar to the above ones while 30 seconds irradiation was necessary to give the same photosensitivity when the solution excluding triphenylbismutin was employed.

In the instant Example, the sensitization effect by tri-' phenylbismutin was able to be measured by the degree of colorization of the solution caused by the light irradiation. That is, when triphenylbismutin is present, the solution was colorized to bluish by the light irradiation for 5 minutes while it took 15 minutes to colorize to bluish in the absence of triphenylbismutin.

When a poly-9-vinylcarbazole obtained by precipitation purification of the poly-9-vinylcarbazole as mentioned inthe above formulation or obtained by precipitation purification of a poly-9-vinylcarbazole obtained 15 by polymerizing vinylcarbazole was employed in place of Luvican M-170 in the instant Example, a minute irradiation can colorize the solutionto bluish while blue colorization was hardly observed and a lowering of photosensitivity was observed with 5 minute irradiation when the solution excluding triphenylbismutin.

When 80 mg. of lenco malachite green was added to the above-mentioned formulation and irradiated for 2 minutes, the exposure amount producing clear positive images for the resulting photosensitive paper was 95 lux.sec.

When 200 mg. of N-vinylcarbazole was added to the above-mentioned formulation and irradiated for 5 minutes, the exposure amount producing clear positive image for the resulting photosensitive paper was 90 lux.sec.

For reference, a photosensitive paper obtained by coating a solution of poly-9-vinylcarbazole above requires an exposure amount of about 60,000 lux.sec. for producing good positive images. A commercially available dye-sensitized zinc oxide photosensitive paper requires about 95 lux.sec. to produce good positive images.

Example 2 Poly-9-vinylcarbazole (Luvican M-l70, trade name, supplied by Badischc Anilin und Soda Fabrik,

A mixture of the above-mentioned ingredients was used to produce a photosensitive paper in a way similar to Example 1, the light irradiation being effected for 5 .minutes. The resulting photosensitive paper was given a uniform negative charge of about 380 V by corona charging by using a charging apparatus of about 5.5

KV, contacted with an original positive film, exposed to a 150 watt tungsten lamp at 200 lux.sec., and soaked in a positive liquid developer to produce clear positive images of high fidelity to the original image.

Following the instant Example except that 400 mg. of tribromomethylsulfone was used in place of carbon tetrabromide and 50 mg. of leuco crystal violet was employed as a dye base compound, an exposure amount for obtaining clear positive images was 190 lux.sec. Further, when 80 mg; of N-methyldiphenylamine was added as an organic colorization component in place of leuco crystal violet in the above procedure, the exposure amount for producing clear images was 180 lux.- sec.

Example 3 Poly-9-vinylcarbazole (Luvican M-170, trade name, supplied by BASF) 8 g The mixture of the above-mentioned ingredients was Example 4 Poly-9-vinylcarbazole (PO-O98, trade name, supplied by Schuchardt) 2 g. Tribromomcthylphenylsulfone 100 mg. Triphcnylbismutin 2 mg. Dioctylphthalate 0.5 g. Chlorobenzcne ml.

A solution composed of the above ingredients was coated on a base paper of 79 g/m which was treated with a hydrophilic polymer so as to inhibit the permeation of a solvent, in an amount of about 5 g/m by a double roll coating method and, after coating is finished, the resulting coating was immediately irradiated by a 500 watt xenon lamp at a distance of about 10 cm for 5 seconds to produce a photosensitive paper. When triphenylbismutin was not used, the required irradiation time was 15 seconds. The resulting photosensitive paper was given a uniform negative charge of about 280 V by corona charging by using a charging device of about 5.5 KV, placed under an original positive film, exposed to a 15 watt tungsten lamp at 150 lux.sec., and soaked in a positive liquid developer to produce a positive image of high fidelity to the original image.

In the following Examples 5 39 the procedures follow Example 1. That is, a solution obtained by mixing the listed ingredients is irradiated with a watt high pressure mercury lamp for 5 minutes, coated on a base paper, and dried to produce a photosensitive paper. The resulting photosensitive paper is subjected to corona charging by a charging device of about 5.5 KV, contacted with an original positive film and exposed to a watt tungsten lamp.

In each of Examples 5 39 there are shown a formulation for the solution, an exposure amount necessary for obtaining clear positive images and, for comparison, an exposure amount necessary for obtaining clear positive images when the organometallic compound is not employed.

Example 5 Poly-3bromo-9vinylcarbazole 8 g. Di-tertiarybutyl-P-oxide 400 mg. 2,7-Bis (dimethylamino)-l0-P-dimethyl aminophenyl-9, 10-dihydro-9, 9-dimethyl Anthraccne 100 mg. triphenylphosphine 8 mg. Monochlorbenzene 200 ml.

The exposure amount needed lux.sec. When triphenylphosphine was not contained, the exposure amount was 350 lux.sec.

Example 6 Copolymer of 3-iodo-9-vinylcarbazole and Example 6-Continued The exposure amount needed 90 lux.sec. When tet- 9-vinylcarbazole (in ratio of raphenyllead was not contained, the exposure amount .4010) 8 w 255lu.

Bromoform 400 mg. as X sec l,2-Dimethylindole lOO mg. E 12 Triphenylphosphine 8 mg. p Benzene 200 ml.

Graft-copolymer of J-vinylcarbazole and ethylacrylate (in the ratio of 90 l0) 8 The exposure amount needed 160 lux.sec. However, Carbon letrabmmide 200 1 when triphenylphosphine was not contained, the expol 0 g g gf f g n 800 0 [1 a sure amount was 390 lux.sec. i g fi 8 I Benzene 200 ml. Example 7 Diphenyl chloride 2 g.

2, 4. 7-trinitro 9-.fluorenone 50 mg.

Poly-9-vinylcarbazole I (PC-098 trade name, supplied by Schuchardt Co.) 8 g. Carbon tetrabromide 400 mg. Triphenylbismmhine 8 mg The exposure amount needed l85 lux.sec. When bls ge zeth k 6 (cyclopentadlenyl) zlrconlum dlbromlde was not conpm tained, the exposure amount was 395 lux.sec.

5 Example 13 The exposure amount needed 90 lux.sec. However, when triphenylbismuthine was not contained, the expo- Copolymer or 3-igd0-9-vinylcarbazolg sure amount was 300 x and 9-vinylcarbazole (in the molar 1 who of 40 60) 8 g. E 8 lodoform 400 mg. p Triphenyl bismuthine 4 mg. Benzene 200 ml. Poly-3-bromo-9-vinylcarbazole 8 g. Trlbromomethylphenylsulfone 400 mg. 2-[ l ,3-Dioxo-hydrinedenyl-(2)] quinoline 50 mg. Cobahocene s, The exposure amount needed 70 lux.sec. When tri- Monochlorbenzene 200 ml. h l t t t d th Methyl violet. 20 mg. p eny lsmu me was no con ame e exposure amount was 250 lux.sec.

Exam le 14 The exposure amount needed 80 lux.sec. When 00- p baltcene was not contamed, the exposure amount was 4 4, dialkylaminobenzyndeneazine r 4 g 280 lux.sec. Copolymer of acrylonitrile and styrene (trade name Estylene AS-6lNT Example 9 supplied by Yahata Kagaku) 4 g- Pentabromodimethylsulfoxide 400 mg. l 4- 2- (3-cthyl-2(3H)- Gmfl'copolymcr 0f g'vmylcarbazPle hcnzothiazolylideneamino) vinyl] and ethylacrylaw 8 40 quinoline 80 mg, Bmmoform 400.1115 Ferrocene 0.1 mg. Leuw methylvmlet 80 Methylene chloride 200 ml. Cobaltcene l 8' Acridine yellow 20 mg. Toluene I 200 Chloranil 70 mg. Dlphcnyl chlorlde 2 g. 2. 4, 7-Trinitro-9-fluorcnone 50 mg The exposure amount needed 380 lux.sec. When fer- The exposure amount needed 140 lux.sec. When corocene was not contamed, the exposure amount was baltcene was not contained, the exposure amount was 325 lux sec v 140 lux.sec.

Example 10 Example 15 I I Nitrated poly-9-vinylcarbazole gglrylla-gl lb'reotmargixllirhyelcarbazole wo rg-g (having 0.0g mollars of nitro radical per one car azo e unit gg l mainly at 3-position of carbazole ring) 8 g. 4 g lodoform I l00 mg. 2.5-l3ls- [4 -dlmethylamlnophenyl-l'] -l. 3, 4-oxadiazole 100 mg. Triphenylarsine 8 mg. The exposure amount needed 95 lux.sec. When tri- Benzene 200 phenylbismuthlne was not contained, the exposure amount was 280 lux.sec. 6O

' Example 1 1 The exposure amount needed 275 lux.sec. When trlphenylarslne was not contained, the exposure Poly -9-vinylcarbazolc (trade name amount was 560 l x Luvlcan M-l70 supplled by BASF) 4008 g. Carbon tetrahromidc mg. 4-'(P-dimethylaminostyryl) EXdmPle l6 qulnoline I 8(8) mg. 5 I Tcuu'phenyucud Poly-3-bromo-9-vlnylcarbazolc 8 g.

Benzene 200 lodoform 400 mg.

Example l6-Continued Example 21 Triphenylphosphine 8 mg.

Nitrobenzene 200 Bis-4,4'-dialkylaminobenzylideneazine 4 g. Methylviolet 20 g- Copolymerization resin of 5 acrylonitrile and styrene (trade name Estylene AS-61NT su lied b Yahata Ka aku) 4 The exposure amount needed 155 lux.sec. When trilffg i 400 ,E

hen l hos hine was not contained the ex osure 4-(4dimethylaminophenylr p y p 1 p 5-(4"-chlorphenyl) imidazole 80 mg. amount was Bis (cyclopentadienyl) tantalum tribromide 16 mg. Example l7 Methylene chloride 200 ml.

Poly-9vinylcarba zole (trad? name M470 The exposure amount needed 870 lux.sec. When his supplied by BASF) 8 g.

Carbon mmbmmide 400 mg (cyclopentadienyl) tantalum tribromide was not con- 1- Methyl-2,5-bis 4'-N,N'- l5 tamed, the exposure amount was 1,880 lux.sec.

diethylaminophenyl-l' -l, 3, 4- E l 22 Triazole 80 mg. xamp 6 Nickelocene 0.5 mg.

Benzene 200 ml.

Nitrated poly-9-vinylcarbazole (having 0.06 mole of nitro radical per one carbazole unit The exposure amount needed 105 lux.sec. When l'B'nalnlyfal 3-position of carbazole ring) 08 g.

romo orm 0 mg. nickelocene was not conta1ned,.the exposure amount Triphenylbismuthine mg was 210 lux.sec. Benzene 200 ml.

Exam le 18 p h D The exposure amount needed 270 lux.sec. When tri- ."l' 4 phenylbismuthine was not contained, the exposure Modified phenol resin I (trade name Beckacite 1100 amount was 530 lux.sec.

supplied by Japan Reichhold Chemical 1nd. Co.) 0 4 g, Example 23 lodoform 400 mg.

l-Ethyl-3- [3-ethyl- 2 (3H-benzoxazolylidine] 11533;; l( glisntalviolet 4 g.

oxyindole 80 mg.

Bis (cyclopentadienyl) niobium (wad? namc Eplkot? I004 .nmmn. 8 m g g. y 52 9 3 zois-iso u y om ne mg. t lil o rz p hthalic anhydride [4lp'dlmethyl amlnophenyl) 1,3-butadienyl] quinoline 80 mg.

' Bis (c clopentadien l) vanadium 4 mg.

3 Y Benzene 200 ml.

The exposure amount needed 830' lux.sec. When his (cyclopentadienyl). niobium tribromide was not conmined, e exposure amount was 5 0 lux.seo 40 The exposure amount needed 2,060 lux.sec. When bis (cyclopentadienyl) vanadium was not contained,

Example 19 the exposure amount was 3,750 lux.sec.

Poly-9-vinylcarbazole Example 24 (trade name Luvican M-l70 supplied y BASF) I 8 Bis-4,4-diallylaminobenzylidene- Iodoform 400 azine 4 F'P w P w 4 Modified phenolic resin 2,4, 7-Trinitro-9-fluorenone mg. (Beckacne 1 [00 trade name Bfmzenc 200 supplied by Japan Reichhold Chemical Co.) 4 g. 'Dlphenyl chlm'ld 2 Tribromomethylphenylsulfone 400 mg.

i 50 l,3,5-Triphenylpyrazoline 80 mg. I Tetraphenyl tin 16 mg.

The exposure amount needed lux.sec. When tri- Chlowbenzene 200 phenylbismuthine was not contained, the exposure amount w 170 l- The exposure amount needed 640 lux.sec. When tet- E l 20 5 raphenyl tin was not contained, the exposure amount r was 1,770 lux.sec.

N,N,N,N'-tetrabenzyl-P-phenylendiamine 4 g. E a l 25 Polyvinylbutylal resin (trade name S-lec ELS supplied by Sekisui Kagaku) 4 g- Poly-Q-vinylcarbazole Hexabromodimethylsulfoxide 400 mg. (L vi M-l70 trad a 3-Ethyl-5- [3-ethyl-2(3H)- supplied by BASF) 8 g. benzothiazolyhdene] rhodanme 60 mg. Tribromomethylsulfone 400 mg. Bis (cyclopentadienyl) chromium 4 mg- Tetraphenyl lead 16 mg.

Toluene 200 ml. Benzene 200 ml.

' The exposure amount needed 1,170 lux.sec. When The exposure amount needed 440 lux.sec. In the abbis (cyclopentadienyl) chromium was not contained, sence of tetraphenyl lead. the exposure amount was the exposure amount' was 1,920 lux.sec. 1,280 lux.sec. I

4 The exposure amount needed 2,300 lux.sec. in the absence of bis (cyclopentadienyl)-P-pentacarbonmonooxide-lzimolybdenum, the exposure amount was 4,150 lux.sec.

Example 27 Leuco malachite green 4 g. Polycarbonate resin (Panlite C, trade name,

suppliedby Teijin) 4 g.

2-Azo-bis-isobutyronitrile 400 mg.

2-(4'-Diethylaminophenyl)-4- J -(4'-dimethylaminophenyl)-5- (2'-chlorophenyl) oxazole 80 mg.

Bis (cyclopentadienyl)-P- hexacarbonmonoxidebitangsten 4 m Methylene chloride 200 ml.

The exposure amount needed 920 lux.sec. In the absence of bis (cyclopentadienyl)-P-hexacarbonmonooxide-bitungsten the exposure amount was 1,650 lux.sec.

Example 28 4,4'-Bis-dimethylamino-benzophenone 4 g. Polycarbonate resin (lupilon E, trade name, supplied by Mitsubishi Edogawa Kagaku) 4 g. Carbon tetrabromide 400 mg. Triphenylbismutin 4 mg.

Methylene chloride The exposure amount needed. 100 lux.sec. In the absence of triphenylbismutin, the exposure amount was 290 lux.sec

Example 29 v Leuco crystal violet Acrylonitrile-styrene copolymer (Estylene AS-6lNT, tradename, supplied by Yahata Kagaku) Z-Azobisisobutyronitrile 3-E thyl--[3-ethyl-2(3H)- benzoxazolylidene] rhodanine Nickelocene Methylene chloride I 4 g.- 400 mg.

vlhqsxr su am u eded 9 la ee. In the absence of nickelocene, the exposure amount was 4,930 lux.sec.

Example 30 Leuco crystal violet 4 g, Epoxy resin (Epikote l 004,- trade name, supplied by Shell Petroleum Co.) 4 g. j Hexabromodimethylsulfoxide 400 mg. 0 tolydine 100 mg. Hydrogenated bis (cyclopentadienyl) rhenium I I 2 mg 22 a The exposure amount needed 750 lux.sec. In the absence of hydrogenated bis (cyclopentadienyl) rhenium, the exposure amount was 1,510 lux.sec.

Example 3 l Bis-4,4' diallylaminobcnzylidene azine. 4 g.

Acrylonitrile-styrene copolymcr (Estylene AS-6lNT. trade name.

supplied Yahata Kagaku) 4 g.

lodoform 400 mg. Bis (cyclopentadienyl) iron dicarbonyl 2 mg. Methylene chloride 200 ml. Acridine yellow 20 mg. Chloranil mg.

The exposure amount needed 520 lux.sec. In the absence of bis (cyclopentadienyl) iron dicarbonyl, the exposure amount was 95.0 lux.sec.

Example 32 Leuco malachite green 4 g.

Polystyrene resin (Piccolastic D-lOO, trade name,

supplied by ESSO) 4 g.

Diphenylthiocarbazone 400 mg.

Vinylcarbazole 50 mg.

' Brominated bis (cyclopentadienyl) cobalt 4 mg.

Benzene ml. 100 ml.

Methylene chloride The exposure amount'needed 2,400 lux.sec. In the absence of brominated bis (cyclopentadienyl) cobalt, the exposure amount was 90,400 lux.sec.

Example 33 phenylenediamine 4 g. Modified phenolic resin (Beckacite 1100, trade name,

supplied by Japan Reichhold Chemical Co.) 4 g. Bromoform 400 mg. Tetraphenyl tin 4 mg. Benzene 200 ml.

The exposure amount needed l,550 lux.sec. In the absence of tetraphenyl tin, the exposure amount was 2,250 lux.sec.

Example 34 Bis-4,4-diallylaminobenzylidene azine 4 g. Modified phenolic resin (Beckacite I100, trade name, supplied by Japan Reichhold Chemical Co.) 4 g. Tribromomethylphenylsulfone 400 mg. Hexaphenylditrn 4 mg. Chlorobenzene 200 ml.

The exposure amount needed 720 lux.sec. In the ab sence of hexaphenylditin, the exposure amount was 1,120 lux.sec.

Example 35 Leuco malachite green 4 g. Polystyrene resin (Piccolastic D-l00, trade name,

supplied by B880) 4 g.

Example 35-Continued Diphenylthiocaroazone 400 mg. Hexaphenylditin 2 mg. Benzene 100 ml. Methylene chloride lOO ml.

I The exposure amount needed 2,300 lux.sec. In the absence of hexaphenylditin, the exposure amount was v 3,750 lux.sec.

Example 36 Leuco crystal violet 4 g. Acrylonitrile-styrene copolymer (E stylene AS-GlNT, trade name, supplied by Yahata Kagaku) 4 g. 2-Azobisisobutyronitrile 400 mg. Ferrocene 0.5 mg. Methylene chloride 200 ml.

The exposure amount needed 600 lux.sec. In the absence of ferrocene, the exposure amount was 2,300 lux.sec.

- Example 37 The exposure amount needed 780 lux.sec. In the absence of tetraphenylgermanium, the exposure amount was 1,450 lux.sec.

Example 38 Poly-9-vinylcarbazole (Luvican M-l70, trade name,

supplied by HASP) 8 g.

Carbon tetrabromide 400 mg. Bis (cyclopentadienyl) cerium 8 mg Dioxane 200 ml The exposure amount needed 100 lux.sec. In the absence of bis (cyclopentadienyl) cerium, the exposure amount was 315 lux.sec.

EXAMPLE 39 Following Example 38, but using his (cyclopentadienyl) titanium, bis (cyclopentadienyl) chromium, bis (cyclopentadienyl) manganese, or dihalogenated bis (cyclopentadienyl) vanadium in place of bis (cyclopentadienyl) cerium, the exposure amount needed was i about 200 lux.sec. for each of them.

Example 40 lodoform 100 mg Triphenylphosphine 4 mg. Benzene 25 ml.

A solution composed of the above ingredients was placed in a. 50 ml. quartz Erlenmeyer flask and irradi- .ated by a high pressure mercury lamp of 100 watt at a distance of 10 cm for about minutes. (When tripoly-3-nitro-9-vinylcarbazole 2 g. diphenyl chloride 0.5 g. benzene 25 ml.

was poured into the above-mentioned Erlenmyer flask and mixed with the contents and allowed to stand for three days in a dark place. Then, the solution was coated on an Al laminate paper of 50 p. thick to form a coating of about 5 u and-dried naturally to form a photosensitive paper. The resulting photosensitive paper was given a uniform negative charge of about 350 V by corona charging by using a charging device of about 5.5 KV, contacted with an original positive film, to a 150 watt tungsten lamp at 150 lux.sec. and soaked in a positive liquid developer to form positive images of high fidelity to the original image.

Example 41 Carbon tetrabromide l00.mg. Vinylcarbazole 50 mg. Triphenylbismutin 2 mg. Benzene 25 ml.

A solution composed of the above ingredients was placed in a 50 ml. quartz Erlenmeyer flask, irradiated with a 500 watt xenon lamp'at a distance of 10 cm for about 5 minutes. When triphenylbismutin was not used,

30'minute irradiation was necessary.

Then, a solution of 2 g. of poly-9-vinylcarbazole (PO- 098, trade name, supplied by Schuchardt) in 25 ml. of benzene was immediately poured into the abovementioned Erlenmeyer flask and the resulting mixture was allowed to stand in a dark place for 3 days. Then the resulting mixture was coated on an Al plate (0.8 mm thick) to form a coating of about 5 11. thick, and dried naturally to form a photosensitive plate. The resulting photosensitive plate was subjected to an electrophotographic process similar to that of Example 40 and an exposure amount of 110 lux.sec. was required to form positive images of high fidelity to the original image.

Example 42 Pentabromodimethylsulfoxide mg. Triphenylbismutin l mg. Xylene 25 mg.

A solution composed of the above ingredients was placed in a 50 ml. quartz Erlenmeyer flask, and irradiated by a 500 watt xenon lamp at a distance of 20 cm for about 10 minutes. When triphenylbismutin was not used, 30 minute irradiation was necessary.

Then, a solution of leuco malachite green 1 g. and

acid was The solution thus obtained was coated on a baryta paper (80 a thick) which had been treated so as to increase the electroconductivity to form a coating of about 5 11. thick and dried naturally to produce a photosensitive paper. The photosensitive paper thus obtained was subjected to an electrophotographic process similar to Example 40 to produce positive images of high fidelity to the original image. The required exposure amount was 350 lux.sec..

Example 43 Poly-9-vinylcarbazole 2 g. Carbon tetrabromide 50 mg.

Triphenylbismutin 2 mg. Benzene 25 ml. lodoform 50 mg.

, Benzene 25 ml.

A solution of (l) and a solutionof (II) were irradiated by a l-watt high pressure mercury lamp at'a distance of about "10 cm for about 5 minutes. (When triphenyl bismutin was not used, the irradiation time was minutes'.) Then, these two solutions were immediately mixed, allowed to stand at a dark place for 10 hours, coated on a polyester film (75 )1. thick) having an aluminum deposit to form a coating of about 5 p. thick and dried naturally to produce a photosensitive film. The photosensitive film thus obtainedwas subjected to an electrophotographic process similar to Example 40, and an exposure amount of 120 lux.sec. was required to produce positive images of high fidelity to the original image.

When a solution of poly-9-vinylcarbazole above was used for producing a photosensitivefilm, an exposure amount of about 58,000 lux.sec. was required to give good positive images.

Example 4.4

PoIy-ii-bromo-Q-vinylcarbazole 2 g. (l) Bromoform 50 mg. chlorobenzene 25 ml. Hcxachloroethane 50 mg. (ll) 7 Triphenylbismutin 2 mg. Chlorobenzene 25 ml.

v The solutions (I) and (II) were irradiated by a 100 watt high pressure mercury lamp at a distance of about 10 cm for 10 minutes. (When triphenylbismutin was not used, the irradiation time required was minutes.)

about 5 a thick followed by natural drying to produce a photosensitive paper. The resulting photosensitive paper was given a uniform negative charge of about 350 V by corona charging by using a charging device of 5.5 KV, contacted with an original positive film, ex-

posed to a 150 watt tungsten lamp at 150 lux.sec., and soaked in a positive liquid developer to produce positive images of high fidelity to the original image.

Example 45 Poly-9-vinylcarbazole (Luvican M-l70, trade name,

The solutions of (l) and (II) were irradiated by a 500 watt xenon lamp at a distance of about 20 cm for about 5 minutes (When triphenylbismutin was not employed, the required irradiation time was 30 minutes). Immediately after the irradiation treatment, these two solu-,

tions were mixed and allowed to stand in a room under. Y

a fluorescent lamp for about 24 hours. Then, 5 ml. of

a solution of 5 mg. Oil pink in benzene as a sensitizing dye was added thereto, and a photosensitive film was produced in a way similar to Example 44 and subjected nal image.

to an electrophotographic process similar to Example 44. An exposure amount of 120 lux.sec. was required to produce a positive image of high fidelity to the origi- Example 46 Poly-9-vinylcarbazole (PO 098, trade name,

supplied by Schuchardt) I g. Carbon tetrabromide 10 g. Triphenylbismutin 340 mg. Diphenyl chloride 30 g. Benzene 5 ml.

A solution composed of the above ingredients was coated on a base paper of 60 g/m (the surface on which the solution is applied was treated with a hydrophilic polymer so as to inhibit the permeation of a solvent) in an amount of about 6 g/m by a kiss roll coating method and then immediately irradiated by a high pressure mercury lamp watt) at a distance of about 15 cm for 10 seconds. When triphenylbismutin was not used, the required irradiation time was 30 seconds. Then, the coating was-dried by hot air at 70C at a wind velocity of 15 m/sec. to produce a photosensitive paper. The resulting photosensitive paper was subjected to an electrophotographic process similar to Example 44 and the required exposure amount for pro- 1 ducing a positive image of high fidelity to the original image was lux.sec.

We claim:

1. An electrophotographic photosensitive member which comprises a support having coated thereon a sensitized layer'of photoconductive photosensitive material, said material'comprising an organic photoconductive material, a free radical former capable of producing free radicals for sensitizing said organic photoconductive material when uniformly excited by radiation energy and an organometallic compound incapable of liberating free radicals under the exposure used to excite said free radical former, but capable of catalyzing the sensitizing ability of the radical former, said photoconductive photosensitive material having been sensitized by applying said radiation energy uniformly to at least said free radical former and said organometallic compound.

2. A photosensitive material according to claim 1 in which the organometallic compound is at least one member selected from the group consisting of alkyl metallic compounds, aryl metallic compounds, and alkylaryl metallic compounds of a metal element of Group IV B or Group V B of the Periodic Table.

3. A photosensitive material according to claim 2 in which the metal element of Group IV B is a member selected from the group consisting of Ge, Sn and Pb.

' 4. A photosensitive material according to claim 2 in which the metal element of Group V B is a member selected from the group consisting of P, As, Sb and Bi.

5. A photosensitive material according to claim 2 in which the aryl metallic compound is one of triphenyl metallic compound and tetraphenyl metallic compound.

6. A photosensitive material according to claim 1 in which the organometallic compound is a cyclopentadienyl metallic compound of at least one transition metal element selected from the group consisting of Group Ill A, IV A, V A, VIA, VII A and VIII A of the Periodic Table.

7. A photosensitive material according to claim 6 in which the transition metal element of Group III A of the Periodic Table is a member selected from the'group consisting of Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Er and Yb.

8. A photosensitive material according to claim 6 in which the transition metal element of Group IV A of the Periodic Table is a member selected from the group consisting of Ti, Zr'and Hf.

9. A photosensitive material according ,to claim 6 in which the transition metal element of Group V A of the Periodic Table is a member selected from the group consisting of V, Nd and Ta.

10. A photosensitive material according to claim 6 in which the transition metal element of Group VI A is a member selected from the group consisting of Cr, Mo, .W and U.

11. A photosensitive material according to claim 6 in which the transition metal element of Group VII A is a member selected from the group consisting of Mn, To and Re.

12. A photosensitive material according to claim 6 in which the transition metal element of Group VIII A is a member selected from the group consisting of Fe, Co, Ni and Ru.

13. A photosensitive material according to claim 1 in which the content of the organometallic compound is 10' 10 percent by weight based on the organic photoconductive material.

14. A photosensitive material according to claim 1 in which the content of the free radical former is l 30 percent by weight based on the-organic photoconductive material. l.

15. A photosensitive material, according to claim 1 in which a sensitizing material is incorporated in a mixture of a free radical former and an organic photoconductive material reactively treated by a radiation energy.

16. A photosensitive material accordingto claim in which the sensitizing material is Lewis acid.

17. A photosensitive material according to claim 15 in which the sensitizing material is a sensitizing dye.

18. A photosensitive material according to claim 15 in which the sensitizing material is a Lewis acid and a sensitizing dye.

19. A photosensitive member according to claim 1 wherein at least one organometallic compound is selected from the group consisting of triphenylbismuthine, triphenylphosphine, tetraphenylarsine, ferrocene and cobaltocene.

20. A photosensitive member according to claim 1 including at least one organic photosensitive material selected from the group consisting of vinyl carbazoles, aromatic amine derivatives, diphenylmethane compoundsand triphenylmethane compounds.

21. A photosensitive material according to claim 20 in which the vinyl carbazole is at least one member selected from the group consisting of poly-9 vinylcarbazole, bromine substituted poly-9- vinylcarbazole and iodine substituted poly-9- vinylcarbazole.

where R is selected from the group consisting of hydrogen, alkyl, chlorine, bromine, iodine,

where R, is selected from the group consisting of substituted or unsubstituted alkyl, aryl and heterocyclic residue; X, Y and Z are, similar or dissimilar, selected from the group consisting of hydrogen, alkyl, Cl, Br and I and at least one of X, Y and Z is halogen atom.

25. A photosensitive material according to claim 24 in which the polyhalogen containing compound is carbon tetrabromide.

26. A photosensitive material according to claim 24 in which the polyhalogen containing compound is bromoform.

27. A photosensitive material according to claim 24 in which the polyhalogen containing'compound is iodoform.

28. A photosensitive material according to claim 24 in which the polyhalogen containing compound is a halogenated organic sulfoxide.

29. A photosensitive material according to claim 24 in which the polyhalogen containing compound is a halogenated organic sulfone compound.

30. A photosensitive member according to claim 1 wherein said free radical former is a polyhalogen containing compound and said organic photoconductive material is a vinylcarbazole.

31. A photosensitive member according to claim 1 including a colorization component selected from the group consisting of a dye base or an organic colorization component capable of forming a coloring material by reaction with said free radical former upon radiation excitation.

32. A photosensitive material according to claim 31 in which the dye base compound is selected from the group consisting of leuco bases, carbinol bases, styryl dye bases, cyanine dye bases, merocyanine dye bases and leuco dihydroanthracenes.

33. A photosensitive material according to claim 32 in which the leuco base is a member selected from the group consisting of leuco bases of triphenylmethane dye and leuco bases of diphenylmethane dye.

34. A photosensitive material according to claim 32 in which the carbinol base is selected from the group consisting of carbinol bases of ,triphenylmethane dye and carbinol bases of diphenylmethane dye.

35. A photosensitive material according to claim 31 in which the organic colorization component is a member selected from the group consisting of arylamines, carbazoles, indoles, 1,3,4-oxadiazoles, 1,3,4-triazoles, imidazoles, pyrazolines, aminophenyl substituted oxazoles, benzidines, l,3-diphenyl-tetrahydroimidazoles,

- phenazines, acridines, acyl hydrazone derivatives, quinoxalines, N-di-substituted amino containing arylideneazines, pyridines, quinolines, ethylene derivatives, and spiropyran compounds.

36. A photosensitive material according to claim 35 in which the arylamine is a compound of the formula:

where R is a member selected from the group consisting of hydrogen, alkyl, aryl and aralkyl (substituted or unsubstituted) and R is a member selected from the group consisting of phenyl, a-naphthyl and B-naphthyl and R is a member selected from the group consisting of alkyl, aryl and aralkyl (substituted or unsubstituted).

37. A photosensitive material according to claim 36 in which the carbazole is a compound of the formula:

I y it where R is a member selected from the group consisting of hydrogen, alkyl, alkenyl, aralkyl and aryl (substituted or unsubstituted) and R, and R are, similar or dissimilar, selected from the group consisting of hydrogen, alkyl, alkenyl, aralkyl, alkoxy, halogen, and dialkylamino.

38. A photosensitive material according to claim 36 in which the indole is a compound of the formula:

Ills

H:Ra

where R is a member selected from the group consisting of hydrogen, alkyl aralkyl and aryl (substituted or unsubstituted) and each R is, similar or dissimilar, selected from thegroup consisting of hydrogen, alkyl, alkoxy, halogen and dialkylamino.

39. An electrophotographic photosensitive member which comprises a support having coated thereon a sensitized layer of photoconductive photosensitive material, said material comprising an organic photoconductive material, a free radical former capable of producing free radicals for sensitizing said organic photoconductive material when uniformly excited by radiation energy having ultraviolet radiation and an organometallic compound incapable of liberating free radicals under the exposure used to excite said free radical former, but capable of catalyzing the sensitizing ability of the radical former, said photoconductive photosensitive material having been sensitized by applying said radiation energy uniformly having ultraviolet radiation to at least said free, radical former and said organometallic compound.

40. The member of claim 29 wherein said photoconductive photosensitive material is sensitized by applying said radiation energy to said organic photoconductive material, said free radical former and said organometallic compound.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,847,607 Dated November 12, 1974 Invent ICHIRO ENDO ET AL.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Title Page, after "Related U.S. Application Data" insert [30] Foreign Application Priority Data 7 February 4 1970 Japan Q .45-9836 February 4, 1970 Japan....... .459838 Aprilll4, 1970 a an. ..45-3l850 Column 4, line l9, "l l" should read m--;

Column 4, line 19, "N" should read n-; Column 5, line 39, "IVa" should read --IVA- "Va" should read -VA--;

Column 8, line 29, m should read Column 11, line 5, "E" should read F-;

Column 23, line 1, "Diphenylthiocaroazone" should read Diphenyl'thiocarbazone--;

Claim 40, line 48, "29" should read 39-.

Signed and sealedthis 4th day of March 1975.

(SEAL) Attest:

- C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Arresting Qfficer and Trademarks FORM po'wso USCOMM-DC wan-Poo t .5. GOVERNMENT FRINTIuG OFFICE 1 l9, U-J"-l34, 

1. AN ELECTROPHOTOGRAPHIC PHOTOSENSITIVE MEMBER WHICH COMPRISES A SUPPORT HAVING A COATED THEREON A SENSITIZED LAYER OF PHOTOCONDUCTIVE PHOTOSENSITIVE MATERIAL, SAID MATERIAL COMPRISING AN ORGANIC PHOTOCONDUCTIVE MATERIAL, A FREE RADICAL FORMER CAPABLE OF PRODUCING FREE RADICALS FOR SENSITIZING SAID ORGANIC PHOTOCONDUCTIVE MATERIAL WHEN UNIFORMLY EXCITED BY RADIATION ENERGY AND AN ORGANOMETALLIC COMPOUND INCAPABLE OF LIBERATING FREE RADICALS UNDER THE EXPOSURE USED TO XCITE SAID FREE RADICAL FORMER, BUT CAPABLE OF CATALYZING THE SENSITIZING ABILITY OF THE RADICAL FORMER, SAID PHOTOCONDUCTIVE PHOTOSENSITIVE MATERIAL HAVING BEEN SENSITIZED BY APPLYING SAID RADIATION ENERGY UNIFORMLY TO AT LEAST SAID FREE RADICAL FORMER AND SAID ORGANOMETALLIC COMPOUND.
 2. A photosensitive material according to claim 1 in which the organometallic compound is at least one member selected from the group consisting of alkyl metallic compounds, aryl metallic compounds, and alkylaryl metallic compounds of a metal element of Group IV B or Group V B of the Periodic Table.
 3. A photosensitive material according to claim 2 in which the metal element of Group IV B is a member selected from the group consisting of Ge, Sn and Pb.
 4. A photosensitive material according to claim 2 in which the metal element of Group V B is a member selected from the group consisting of P, As, Sb and Bi.
 5. A photosensitive material according to claim 2 in which the aryl metallic compound is one of triphenyl metallic compound and tetraphenyl metallic compound.
 6. A photosensitive material according to claim 1 in which the organometallic compound is a cyclopentadienyl metallic compound of at least one transition metal element selected from the group consisting of Group III A, IV A, V A, VI A, VII A and VIII A of the Periodic Table.
 7. A photosensitive material according to claim 6 in which the transition metal element of Group III A of the Periodic Table is a member selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Er and Yb.
 8. A photosensitive material according to claim 6 in which the transition metal element of Group IV A of the Periodic Table is a member selected from the group consisting of Ti, Zr and Hf.
 9. A photosensitive material according to claim 6 in which the transition metal element of Group V A of the Periodic Table is a member selected from the group consisting of V, Nd and Ta.
 10. A photosensitive material according to claim 6 in which the transition metal element of Group VI A is a member selected from the group consisting of Cr, Mo, W and U.
 11. A photosensitive material according to claim 6 in which the transition metal element of Group VII A is a member selected from the group consisting of Mn, Tc and Re.
 12. A photosensitive material according to claim 6 in which the transition metal element of Group VIII A is a member selected from the group consisting of Fe, Co, Ni and Ru.
 13. A photosensitive material according to claim 1 in which the content of the organometallic compound is 10 3 - 10 percent by weight based on the organic photoconductive material.
 14. A photosensitive material according to claim 1 in which the content of the free radical former is 1 - 30 percent by weight based on the organic photoconductive material.
 15. A photosensitive material according to claim 1 in which a sensitizing material is incorporated in a mixture of a free radical former and an organic photoconductive material reactively treated by a radiation energy.
 16. A photosensitive material according to claim 15 in which the sensitizing material is Lewis acid.
 17. A photosensitive material according to claim 15 in which the sensitizing material is a sensitizing dye.
 18. A photosensitiVe material according to claim 15 in which the sensitizing material is a Lewis acid and a sensitizing dye.
 19. A photosensitive member according to claim 1 wherein at least one organometallic compound is selected from the group consisting of triphenylbismuthine, triphenylphosphine, tetraphenylarsine, ferrocene and cobaltocene.
 20. A photosensitive member according to claim 1 including at least one organic photosensitive material selected from the group consisting of vinyl carbazoles, aromatic amine derivatives, diphenylmethane compounds and triphenylmethane compounds.
 21. A photosensitive material according to claim 20 in which the vinyl carbazole is at least one member selected from the group consisting of poly-9-vinylcarbazole, bromine substituted poly-9-vinylcarbazole and iodine substituted poly-9-vinylcarbazole.
 22. A photosensitive material according to claim 20 in which the vinyl carbazole is a member selected from the group consisting of 9-vinylcarbazole copolymer, bromine substituted 9-vinylcarbazole copolymer and iodine substituted 9-vinyl-carbazole copolymer.
 23. A photosensitive member according to claim 1 including at least one free radical former selected from the group consisting of polyhalogen containing compound, carbonyl compound, organic sulfur compound, peroxide, azo compound, and diazo compound.
 24. A photosensitive material according to claim 23 in which the poly-halogen containing compound is a compound of the formula
 25. A photosensitive material according to claim 24 in which the polyhalogen containing compound is carbon tetrabromide.
 26. A photosensitive material according to claim 24 in which the polyhalogen containing compound is bromoform.
 27. A photosensitive material according to claim 24 in which the polyhalogen containing compound is iodoform.
 28. A photosensitive material according to claim 24 in which the polyhalogen containing compound is a halogenated organic sulfoxide.
 29. A photosensitive material according to claim 24 in which the polyhalogen containing compound is a halogenated organic sulfone compound.
 30. A photosensitive member according to claim 1 wherein said free radical former is a polyhalogen containing compound and said organic photoconductive material is a vinylcarbazole.
 31. A photosensitive member according to claim 1 including a colorization component selected from the group consisting of a dye base or an organic colorization component capable of forming a coloring material by reaction with said free radical former upon radiation excitation.
 32. A photosensitive material according to claim 31 in which the dye base compound is selected from the group consisting of leuco bases, carbinol bases, styryl dye bases, cyanine dye bases, merocyanine dye bases and leuco dihydroanthracenes.
 33. A photosensitive material according to claim 32 in which the leuco base is a member selected from the group consisting of leuco bases of triphenylmethane dye and leuco bases of diphenylmethane dye.
 34. A photosensitive material according to claim 32 in which the carbinol base is selected from the group consisting of carbinol bases of triphenylmethane dye and carbinol bases of diphenylmethane dye.
 35. A photosensitive material according to claim 31 in which the organic colorization component is a member selected from the group consisting of arylamines, carbazoles, indoles, 1,3,4-oxadiazoles, 1,3,4-triazoles, imidazoles, pyrazolines, aminophenyl substituted oxazoles, benzidines, 1,3-diphenyl-tetrahydroimidazoles, pHenazines, acridines, acyl hydrazone derivatives, quinoxalines, N-di-substituted amino containing arylideneazines, pyridines, quinolines, ethylene derivatives, and spiropyran compounds.
 36. A photosensitive material according to claim 35 in which the arylamine is a compound of the formula:
 37. A photosensitive material according to claim 36 in which the carbazole is a compound of the formula:
 38. A photosensitive material according to claim 36 in which the indole is a compound of the formula:
 39. An electrophotographic photosensitive member which comprises a support having coated thereon a sensitized layer of photoconductive photosensitive material, said material comprising an organic photoconductive material, a free radical former capable of producing free radicals for sensitizing said organic photoconductive material when uniformly excited by radiation energy having ultraviolet radiation and an organometallic compound incapable of liberating free radicals under the exposure used to excite said free radical former, but capable of catalyzing the sensitizing ability of the radical former, said photoconductive photosensitive material having been sensitized by applying said radiation energy uniformly having ultraviolet radiation to at least said free radical former and said organometallic compound.
 40. The member of claim 29 wherein said photoconductive photosensitive material is sensitized by applying said radiation energy to said organic photoconductive material, said free radical former and said organometallic compound. 